Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
  • C07D487/18—Bridged systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the present invention relates to a composition of cyclic sterically hindered amine stabilizers with 4 pending 2,2,6,6-tetramethyl-piperidine groups. These groups are substituted at the nitrogen atom by 2 to 4 substituents in a specific ratio. Further aspects of the invention are the individual components, an agricultural polymeric article containing such a composition, a process for stabilizing a polymeric article and the use of the composition as stabilizer and flame retardant.
• HAS Sterically hindered amines
• primary or secondary not sterically hindered amines may be present as reaction by products in some commercially available HAS. These by products can negatively influence the stabilizing efficiency.
• Chimassorb 966 is a commercial sterically hindered amine stabilizer, which does not have this problem because primary or secondary not sterically hindered amines are principally not present in its macrocyclic structure.
• US 4442250 discloses such hindeved amine stabilizers used as light, heat or oxidation stabilisers for synthetic polymers.
• Chimassorb 966 is higher than 290°C.
• processing temperature of polymers, in particular polyolefins is below 290°C.
• Chimassorb 966 when used as polyolefin stabilizer will not or not completely melt during processing.
• films stabilized with Chimassorb 966 could be affected by a high number of gels due to unmelted spots.
• the use of Chimassorb 966 as stabilizer in film applications where high numbers of gels are undesired causes problems.
• One aspect of the invention is a composition comprising
• the total amount of components b-I to b-IV is from 0.01 to 1 % by weight, relative to the weight of the natural or synthethic polymer
• Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
• C 1 -C 20 alkoxy G 11 is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.
• C 3 -C 12 cycloalkoxy is, for example, cyclopropoxy, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.
• Any C 5 -C 12 cycloalkyl substituents are, in particular, cyclopentyl and cyclohexyl.
• C 7 -C 9 phenylalkyl is preferably benzyl.
• Suitable natural or synthetic polymers are given below.
• Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• biodegradable polymers are used in the present invention. Examples for such polymers are given below.
• Biodegradable polymers of either natural or synthetic origin include but are not limited to Polyethylensuccinate (Lunare SE (Nihon Shokubai)), Polybutylensuccinate (Bionolle 1000 (Showa Highpolymer)), Polybutylensuccinate/adipate (Bionolle 3000 (Showa Highpolymer)) Polybutylensuccinate/carbonate (lupec (Mitsubishi Gas Chemicals)), Polybutylensuccinate/terephtalate (Biomax (Dupont), Ecoflex (BASF), EasterBio (Eastman Chemicals)) Polycaprolactone (CelGreen PH (Daicel Kagaku), Tone (UCC)) Poly(hydroxyalkanoates) (Nodax from Procter and Gamble or from Metabolix), Poly 3-hydroxybutyrate (Biogreen (Mitsubishi Gas Chemicals)) Polylactic acid (NatureWorks (Cargill), LACEA (Mits
• thermoplastic polymers are particularly preferred.
• polyolefins as mentioned under items 1 to 3 above.
• the R 1 are C 4 -C 12 alkyl, C 4 -C 12 alkoxy, C 5 -C 6 cycloalkoxy.
• the compounds of formula (I) may be prepared from the corresponding amine precursors (R 1 is H) which are known and, for example, described in US 4,442,250 .
• the amine precursor is a commercial product, Chimassorb® 966, sold by Ciba Inc.
• the oxidation may be carried out in analogy to the oxidation of 4-hydroxy-2,2,6,6-tetramethylpiperidine described in US 5,654,434 with hydrogen peroxide.
• Another also suitable oxidation process is described in WO 00/40550 using peracetic acid.
• the oxidation must not be carried out until all piperidine nitrogen atoms are oxidized. It can be stopped at many stages before, thus leading to a product mixture which contains NH, NOH and NO ⁇ moieties.
• a further aspect of the invention is a compound of formula (Ia) wherein in formula (Ia) 2, 3 or 4 of the radicals R 1 are C 4 -C 20 alkyl, C 4 -C 20 alkoxy, C 3 -C 12 cycloalkoxy or a group of the formula and the remaining radicals R 1 are hydrogen, oxygen or hydroxyl; the radicals R 2 and R 3 in formulae (Ia) are independently of one another hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl unsubstituted or substitiuted by 1 to 3 C 1 -C 4 alkyl; phenyl unsubstituted or substituted by 1 to 3 radicals selected from -OH and C 1 -C 10 alkyl; C 7 -C 9 phenylalkyl unsubstitted or substituted on the phenyl by 1 to 3 radicals selected from -OH and C 1 -C 10 alkyl; or a group of the formula (I-
• a stabilizer composition comprising a product mixture containing components b-I, b-II, b-III and b-IV; component b-I being a compound of formula (I) with a degree of substitution of 1 in an amount of from 5 to 25 parts by weight, component b-II being a compound of formula (I) with a degree of substitution of 2 in an amount of from 5 to 35 parts by weight, component b-III being a compound of formula (I) with a degree of substitution of 3 in an amount of from 10 to 45 parts by weight and component b-IV being a compound of formula (I) with a degree of substitution of 4 in an amount of from 10 to 45 parts by weight, the sum of the parts of components bl to bIV being 100; formula (I) being wherein the radicals R 1 are C 4 -C 20 alkyl, C 4 -C 20 alkoxy, C 3 -C 12 cycloalkoxy or a group of the formula wherein for component b-I
• additives of the invention and optional further components may be added to the polymer material individually or mixed with one another. If desired, the individual components can be mixed with one another before incorporation into the polymer for example by dry blending, compaction or in the melt.
• the incorporation of the additives of the invention and optional further components into the polymer is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil.
• the additives of the invention and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additve or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc), e.g. as a dry mixture or powder or as solution or dispersion or suspension or melt.
• the incorporation can be carried out in any heatable container equipped with a stirrer, e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
• a stirrer e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
• the incorporation is preferably carried out in an extruder or in a kneader. It is immaterial whether processing takes place in an inert atmosphere or in the presence of oxygen.
• the addition of the additive or additive blend to the polymer can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
• processing machines are single-screw extruders, contrarotating and corotating twin-screw extruders, planetary-gear extruders, ring extruders or cokneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
• the screw length is 1 - 60 screw diameters, preferably 20-48 screw diameters.
• the rotational speed of the screw is preferably 1 - 800 rotations per minute (rpm), very particularly preferably 25 - 400 rpm.
• the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
• the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
• the additives of the invention and optional further additives can also be added to the polymer in the form of a masterbatch ("concentrate") which contains the components in a concentration of, for example, 1% to 40% and preferably 2 % to 20 % by weight incorporated in a polymer.
• concentration a masterbatch
• the polymer must not be necessarily of identical structure than the polymer where the additives are added finally.
• the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
• Suitable furthers additives are the following.
• the final product can be any type of plastic product, which needs stabilization in natural sunlight and/or humidity at low, ambient or elevated temperature.
• the polymer component may be used to manufacture plastic films, sheets, bags, bottles, styrofoam cups, plates, utensils, blister packages, boxes, package wrappings, plastic fibers, tapes, agricultural articles such as twine agricultural films, mulch films, small tunnel films, banana bags, direct covers, nonwoven, pots for agricultural use, goetextiles, landfill covers, industrial covers, waste covers, temporary scaffolding sheets, building films, silt fences, poultry curtains, films for building temporary shelter constructions, disposable diapers, disposable garments.
• the articles may be manufactured by any process available to those of ordinary skill in the art including, but not limited to, extrusion, extrusion blowing, film casting, film blowing, calendering, injection molding, blow molding, compression molding, thermoforming, spinning, blow extrusion and rotational casting.
• a preferred article is an agricultural article made of
• Yet a further aspect of the invention is the use of a composition as defined above for the stabilization of a natural or synthethic polymer against degradation induced by light, heat or oxidation and the use of a said composition as a flame retardant for a natural or synthetic polymer.
• a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 50.0 g of Chimassorb 966, 500 ml of 1,2-dichlorobenzene, 2.5 g of Molybdenum(VI) oxide and 50.0 g of tert-butyl hydroperoxide 70% solution in water.
• the reaction mixture is then heated under stirring to azeotropic temperature removing the water in 4 hours by means of Marcusson apparatus.
• reaction mixture is transferred in a 1 L autoclave and 200 ml of cyclohexane, 50.0 g of tert-butyl hydroperoxide 70% solution in water and 2.5 g of Molybdenum(VI) oxide are subsequently added.
• the reaction is then heated to 140°C and left to react under stirring 4 hours.
• the mixture is then cooled to room temperature and filtered. 300 ml of water and 100.0 g of sodium sulfite are added to the crude filtered solution maintained under stirring.
• the organic phase is then separated and concentrated under vacuum.
• a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 50.0 g of Chimassorb 966, 500 ml of 1,2-dichlorobenzene, 2.5 g of Molybdenum(VI) oxide and 50.0 g of tert-butyl hydroperoxide 70% solution in water.
• the reaction mixture is then heated under stirring to azeotropic temperature removing the water in 4 hours by means of Marcusson apparatus.
• reaction mixture is transferred in a 1 L autoclave and 200 ml of n-octane, 50.0 g of 70% solution of tert-butyl hydroperoxide in water and 2.5 g of Molybdenum(VI) oxide are subsequently added.
• the reaction is then heated to 140°C and left to react under stirring 4 hours.
• the mixture is then cooled to room temperature and filtered. 300 ml of water and 100.0 g of sodium sulfite are added to the crude filtered solution maintained under stirring.
• the organic phase is then separated and concentrated under vacuum.
• a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 50.0 g of Chimassorb 996, 200 ml of 1,2-dichlorobenzene, 23.0 g of potassium carbonate, 1.0 g of potassium iodide and 56.0 g of 1-bromo octane.
• the mixture is maintained under stirring for 18 hours at reflux temperature.
• 200 ml of water are added to the cooled reaction solution and the organic phase is then separated and concentrated under reduced pressure.
• a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 50.0 g of Chimassorb 996, 200 ml of 1,2-dichlorobenzene, 23.0 g of potassium carbonate, 1.0 g of potassium iodide and 56.0 g of 1-bromo decane.
• the mixture is maintained under stirring for 10 hours at reflux temperature.
• 200 ml of water are added to the cooled reaction solution and the organic phase is then separated and concentrated under reduced pressure.
• Example 5 Synthesis of compound 105 starting from Chimassorb 966.
• a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 50.0 g of Chimassorb 996, 250 ml of 1,2-dichlorobenzene, 23.0 g of potassium carbonate, 1.0 g of potassium iodide and 63.0 g of 1-dodecyl bromide.
• the mixture is maintained under stirring for 35 hours at reflux temperature.
• the filtered solution is recrystallized with ethanol and exsiccated under reduced pressure.
• Compound A can be prepared according to the procedure reported in WO 2002058844 t or by means of state of the art oxidation procedures.
• a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 100.0 g of compound A, 500 ml of dichloromethane, 147.0 g of dodecyl aldehyde, 60.0 g of acetic acid and 3.0 g of copper(I) chloride.
• 80.0 g of 30% hydrogen peroxide solution in water are added dropwise to the stirred mixture maintaining the temperature less than 37 °C.
• the reaction is left to react 19 hours at 37°C and after that 30% sodium hydroxide solution is added to the mixture until the pH of the water phase is 11.
• the organic phase is separated from the water phase, washed twice with water and concentrated under vacuum.
• a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 50.0 g of compound A, 200 ml of dichloromethane, 73.5 g of 2-ethylcapronaldehyde, 30.0 g of acetic acid and 1.5 g of copper(I) chloride.
• compound A 200 ml of dichloromethane
• 2-ethylcapronaldehyde 73.5 g of 2-ethylcapronaldehyde
• acetic acid 30.0 g of acetic acid
• copper(I) chloride 1.5 g
• 40.0 g of 30% hydrogen peroxide solution in water are added dropwise to the stirred mixture in 1 hour and 30 minutes maintaining the temperature less than 39°C.
• the reaction is left to react 19 hours at 39°C and after that 30% sodium hydroxide solution is added to the mixture until the pH of the water phase is 11.
• Example 8 Synthesis of compound (108) starting from Chimassorb 966 and compound (B).
• a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 50.0 g of Chimassorb 966, 500 ml of chloro-benzene, 109.0 g of compound (B), 34.5 g of potassium carbonate and 6.9 g of potassium iodide.
• the mixture is maintained under stirring for 16 hours at reflux temperature.
• water is added to the filtered solution and the organic phase is separated and concentrated under vacuum.
• the residue is washed with ethanol and subsequently with water.
• the formed precipitated is filtered and exsiccated in oven.
• Example 9 Alternative synthesis of compound (102) starting from compound (A).
• N°gels/m2 in the additivated LDPE films is counted with Film Scan FS3, sold by OCS Optical Control System. Results are reported in Table 2.
• Carbonyl Increment Evaluation of the carbonyl band increment (1710 cm-1) in LDPE films additivated at 0.4% with compound are under applicative tests to assess the performances as light/heat stabilizers. Stabilizer Performances of compounds 105 and 107 are depicted in the Tables 3 to 6.
• Table 3 Carbonyl Increment of 150 ⁇ m additivated LDPE films upon WOM exposure Time of exposure (h) Film 0 540 1010 1530 3070 5130 Film 6 (0.4% Tinuvin NOR 371) 0.000 0.010 0.022 0.032 0.059 0.114 Film 5 (0.4% compound 107) 0.000 0.006 0.017 0.032 0.059 0.108
• Table 4 Elongation % at break of 150 ⁇ m additivated LDPE films upon WOM exposure Time of exposure (h) Film 0 1030 1765 3060 4380 Film 6 (0.4% Tinuvin NOR 371) 100 92 91 77 66 Film 5 (0.4% compound 107) 100 100 88 88 65
• Table 5 Carbonyl Increment of 150 ⁇ m additivated LDPE films upon WOM exposure Time of exposure (h) Film 0 1091 2225 2910 3760 5110 Film 6 (0.4% Tinuvin NOR 371) 0.000 0.016 0.026 0.033 0.043 0.051 Film 7
• Table 1 flame test on 200 ⁇ m pressed films according to DIN 4102-B2, edge ignition, 40 mm flame, data ex PDR100388)

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)
• Fireproofing Substances (AREA)

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• 2010
  • 2010-01-26 WO PCT/EP2010/050875 patent/WO2010089230A1/en active Application Filing
  • 2010-01-26 ES ES10701030T patent/ES2435468T3/es active Active
  • 2010-01-26 US US13/146,942 patent/US8524812B2/en not_active Expired - Fee Related
  • 2010-01-26 EP EP10701030.8A patent/EP2393876B1/en not_active Not-in-force
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